Treating agent materials

ABSTRACT

A treating agent composition for increasing the hydrophobicity of an organosilicate glass dielectric film when applied to said film. It includes a component capable of alkylating or arylating silanol moieties of the organosilicate glass dielectric film via silylation, and an activating agent which may be an acid, a base, an onium compound, a dehydrating agent, and combinations thereof, and a solvent or mixture of a main solvent and a co-solvent.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation in part of U.S. patent applicationSer. No. 10/940,686, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns a treating agent composition for organosilicateglass dielectric films. More particularly, the invention pertains to amethod for restoring hydrophobicity to the surfaces of organosilicateglass dielectric films which have been subjected to an etching or ashingtreatment in such a way as to remove at least a portion of previouslyexisting carbon containing moieties, resulting in a film having reducedhydrophobicity. These treated films are used as insulating materials inthe manufacture of semiconductor devices such as integrated circuits(“ICs”), in order to ensure low dielectric constant and stabledielectric properties in these films. The compositions include a silanebased monomer with reactive leaving groups, an activating agent whichmay be an acid, a base, an onium compound, a dehydrating agent, andcombinations thereof and a solvent or mixture of a main solvent and aco-solvent.

2. Description of the Related Art

As semiconductor devices scale to lower technology nodes, therequirement for lower and lower dielectric constant (k) has beenidentified to mitigate RC delay. Similarly, as feature sizes inintegrated circuits are reduced, problems with power consumption andsignal cross-talk have become increasingly difficult to resolve. Toachieve lower k (2.6-3.0) in dense inorganic materials, carbon has beenadded to reduce the polarizability thus reducing k. To achieve ultra lowk (<2.4) materials, porosity is added to the carbon-rich dense matrix.While the introduction of carbon and porosity have reduced k, newchallenges during back end of the line processing have also beenidentified. Specifically during etching and ashing, reactive gases havebeen found to damage the carbon at the surface of dense materials.Porous low k's have even more catastrophic effects from reactive etchand ash gases due to diffusion through the film, which causes a greaterextent of damage at the internal pore walls. Once the carbon has beendamaged, the films rehydroxylate and hydrogen bond with water. Becausewater has a dielectric constant of 70, small amounts that are absorbedfor porous materials and adsorbed for dense materials cause thedielectric constant to go up significantly. Also, porous materials tendto void after copper annealing due to the high tensile stress fieldswhich will destroy device yields. None of these are acceptable and leadto unviable materials.

It is believed that the integration of low dielectric constant materialsfor interlevel dielectric (ILD) and intermetal dielectric (IMD)applications will help to solve these problems. While there have beenprevious efforts to apply low dielectric constant materials tointegrated circuits, there remains a longstanding need in the art forfurther improvements in processing methods and in the optimization ofboth the dielectric and mechanical properties of such materials. Devicescaling in future integrated circuits clearly requires the use of lowdielectric constant materials as a part of the interconnect structure.Most candidates for low dielectric constant materials for use in sub-100nm generation ICs are carbon containing SiO₂ films formed by either CVDor spin-on methods. During subsequent processing steps, such as plasmaetching and photoresist removal using plasma or wet strip methods,significant damage occurs to these low-k materials, that causes fluorineaddition and carbon depletion from the low-k material adjacent to theetched surface. In addition to a higher effective k, the resultantstructures are susceptible to void formation, outgassing and blisterformation. The voids in turn may cause an increase in leakage current atelevated voltages and reduction in breakdown voltage. The presentinvention describes a way to reduce the damage and resulting issues bytreating the wafers with silylating agents after the damage is caused.The use of non-damaging ash chemistry, such as H₂/He has been reportedto reduce carbon depletion and associated problems. In this regard, seeI. Berry, A. Shiota, Q. Han, C. Waldfried, M. Sekiguchi, and O.Escorcia, Proceedings—Electrochemical Society, 22, 202 (2002); and A.Matsushita, N. Ohashi, K. Inukai, H. J. Shin, S. Sone, K. Sudou, K.Misawa, I. Matsumoto, and N. Kobayashi, Proceedings of IEEEInternational Interconnect Technology Conference, 2003, 147 (2003).Alternatively, post-ash treatments that replenish carbon have also beenshown to restore hydrophobicity and lower the dielectric constant.Post-ashing treatments that replenish carbon have also been shown torestore hydrophobicity and lower dielectric constant. In this regard,see Y. S. Mor, T. C. Chang, P. T. Liu, T. M. Tsai, C. W. Chen, S. T.Yan, C. J. Chu, W. F. Wu, F. M. Pan, W. Lur; and S. M. Sze, Journal ofVacuum Science & Technology, B, 2 (4), 1334 (2002); and P. G. Clark, B.D. Schwab, and J. W. Butterbaugh, Semiconductor International, 26 (9),46 (2003). An advantage of the later approach is that it allows the useof well-established etching and ashing processes. To this end, it wouldbe desirable to repair damage caused to a porous SiCOH-based low-kmaterial using a post-ash treatment.

One way to approach this challenge is to repair the damaged area ondense surfaces, or in the case of porous materials on the internal porewalls with a re-methylating compound called a treating agent (TA).Treating agents react with the damaged re-hydroxylated surfaces andre-alkylate or re-arylate them which in-turn restores the dielectricconstant. The following reaction describes the an exemplaryre-methylation process: SiOH (damaged surface)+RxSi(OCOCH₃)y (TA) yieldsSiOSiRx (repaired surface)+(CH₃COOH)y (acetic acid). In the case ofporous damaged internal pore wall surfaces, the re-methylation preventsvoid formation. Many times, the use of a treating agent allows forconventional etch and ash processes to be utilized with low and ultralow dielectric constant materials. The treatment could result inreplenishment of carbon to the low-k film, thereby restoringhydrophobicity and resistance to further damage during a wet cleaningoperation. Additionally, it would be desirable if the repaired low-kmaterial was found to be resistant to void formation, which generallyoccurs in untreated porous low-k inter-level dielectric regions duringcopper annealing processes. Silylating agents (“treating agents”) canmethylate the surface of SiO₂ based materials. Contemplated exposureincludes vapor exposure (with or without plasma), spin coating andsupercritical CO₂. Normally, SiCOH based porous low-k materials aresusceptible to void formation in ILD during Cu damascene processing.After a treating agent treatment, the resulting structure issignificantly more resistant to void formation. Without being bound toany specific theory or mechanism, it is believed that plasma damagecauses carbon depletion in the dielectric, by replacing Si—CH₃ bondswith Si—OH bonds. In damaged porous dielectrics, the pore surface is nowcovered with Si—OH bonds. In the presence of tensile stress (such asafter Cu annealing), adjacent Si—OH groups can condense, thus causinglocal densification. The evolving reaction products and the stretchingof the molecules due to the new links formed, causes voids to occur nearthe enter of the ILD space. Treating agents prevent void formation byreplacing most Si—OH bonds by Si—O—Si-Rx bonds, which avoid condensationreactions. Therefóre void formation does not occur.

In addition, it is also known that existence of the SiO—SiR₂—OSi linkage(where the SiR₂ is one example of a treating functionality within thematrix), that the modulus of the porous material should improve. Modulusretention and improvement is required for most porous materials towithstand imposed stresses. The treating linkage studied, adimethylsilyl linkage, clearly improves the modulus. If applied toweakened areas of the silicate, an improvement of the material toexternal stress is expected.

The treating agent composition treatment performed after dielectrictrench and via formation and etching and ashing steps repairs carbondepletion and damage to the low-k materials. By this means, voids aredeterred and the later can withstand internal stresses caused byannealing treatments to the metal filling the trenches and vias.

The treating agent composition treatment is conducted by exposing thewafer surface to the silylating agent in liquid or gas form for a periodsufficient to complete the reaction with the damaged low-K region.Optionally, a high temperature bake can be performed to remove remainingsolvent and excess treating agent. Also, optionally, a wet cleaningoperation can be performed immediately after the treating agentapplication, or after the baking step, using a commercially availablechemical compatible with the low-k dielectric. Additionally adehydration bake may be performed before the treating agent treatment,to increase effectiveness of the treating agent treatment.

The effectiveness of the treating agent treatment can be verified usingunpatterned low-k dielectric films subjected to etching and ashingprocessing followed by the treating agent treatment. A successfultreating agent treatment results in increased carbon concentration thatcan be measured by FTIR, EDX, or XPS techniques. Additionally, a watercontact angle increase is seen, which demonstrates the hydrophobicnature of the post-treatment surface. The treating agent treated filmalso shows a lower dielectric constant extracted from C-V measurements,compared to an etched/ashed film that is not treated with treatingagent. In patterned wafers, the effectiveness of the treating agenttreatment is demonstrated by reduction or elimination of voids in thelow-k dielectric in narrow spaces between Cu trenches after a copperanneal treatment following electroplating of copper, and also by lowerprofile change in trenches or vias after exposure to reactive solvents.

It has been found that treating agents are made by using silane basedmonomers with reactive leaving groups together with an activating agentwhich may be an amine, an onium compound, an alkali metal hydroxide, orcombinations thereof.

In one embodiment of the invention the composition further comprises asolvent which comprises ethylacetoacetate, methyl acetoacetate, t-butylacetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzylacetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthylacetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzylacetate, dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1,2-dichlorobenzene, chlorotoluene,1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or combinationsthereof.

In another embodiment of the invention the composition further comprisesa mixture, preferably a miscible mixture of a main solvent and aco-solvent, which mixture is capable of solubilizing the componentcapable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation and the activatingagent; which co-solvent has a higher vapor pressure and/or boiling pointthan the main solvent.

SUMMARY OF THE INVENTION

The invention provides a composition for treating an organosilicateglass dielectric film which comprises

a) a component capable of alkylating or arylating silanol moieties of anorganosilicate glass dielectric film via silylation,

b) an activating agent and

c) a mixture of a main solvent and a co-solvent, wherein the mixturesolubilizes the component capable of alkylating or arylating silanolmoieties of the organosilicate glass dielectric film via silylation andthe activating agent; and wherein the co-solvent has a higher vaporpressure and/or boiling point than the main solvent.

The invention also provides a composition for treating an organosilicateglass dielectric film which comprises

a) a component capable of alkylating or arylating silanol moieties ofthe organosilicate glass dielectric film via silylation,

b) an activating agent; and

c) a solvent which solubilizes the component capable of alkylating orarylating silanol moieties of the organosilicate glass dielectric filmvia silylation, and the activating agent, which solvent comprisesethylacetoacetate, methyl acetoacetate, t-butyl acetoacetate,2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate,nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthyl acetate,2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate,dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,1,2-dichlorobenzene, chlorotoluene, N,N-diethylacetamide,N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.

The invention further provides a method which comprises:

a) forming an organosilicate glass dielectric film;

b) contacting the organosilicate glass dielectric film with acomposition which comprises a component capable of alkylating orarylating silanol moieties of the organosilicate glass dielectric filmvia silylation; an activating agent; and a solvent which comprises (i)or (ii):

-   -   (i) a mixture of a main solvent and a co-solvent, which mixture        is capable of solubilizing the component capable of alkylating        or arylating silanol moieties of the organosilicate glass        dielectric film via silylation and the activating agent; which        co-solvent has a higher vapor pressure and/or boiling point than        the main solvent;    -   (ii) ethylacetoacetate, methyl acetoacetate, t-butyl        acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,        benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl        acetate, phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl        acetate, alpha-methylbenzyl acetate, dimethylsulfoxide,        N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,        N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,        N,N-diethylacetamide, N,N-diphenylacetamide,        N,N-dimethypropionamide, N,N-dimethylisobutyramide, 1-hexanol,        2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,        1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,        6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or        combinations thereof.

The invention still further provides a method for deterring theformation of stress-induced voids in an organosilicate glass dielectricfilm on a substrate, which organosilicate glass dielectric film has beensubjected to at least one step which removes at least a portion ofpreviously existing carbon containing moieties or reduces hydrophobicityof said organosilicate glass dielectric film, comprising contacting theorganosilicate glass dielectric film, after being subjected to at leastone step which removes at least a portion of previously existing carboncontaining moieties or reduces hydrophobicity of said organosilicateglass dielectric film, with a composition at a concentration and for atime period effective to restore at least some of the carbon containingmoieties hydrophobicity or increase the hydrophobicity of theorganosilicate glass dielectric film, wherein the composition comprises:

a) a component capable of alkylating or arylating silanol moieties of aorganosilicate glass dielectric film via silylation,

b) an activating agent and

c) a solvent which comprises (i) or (ii):

-   -   (i) a mixture of a main solvent and a co-solvent, which mixture        is capable of solubilizing the component capable of alkylating        or arylating silanol moieties of the organosilicate glass        dielectric film via silylation and the activating agent; which        co-solvent has a higher vapor pressure and/or boiling point than        the main solvent;    -   (ii) ethylacetoacetate, methyl acetoacetate, t-butyl        acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,        benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl        acetate, phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl        acetate, alpha-methylbenzyl acetate, dimethylsulfoxide,        N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,        N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,        N,N-diethylacetamide, N,N-diphenylacetamide,        N,N-dimethypropionamide, N,N-dimethylisobutyramide, 1-hexanol,        2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,        1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,        6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or        combinations thereof.

The invention still further provides a method for forming amicroelectronic device which comprises:

a) forming an organosilicate glass dielectric film on a substrate;

b) subjecting the organosilicate glass dielectric film to at least onestep which removes at least a portion of previously existing carboncontaining moieties or reduces hydrophobicity of said organosilicateglass dielectric film;

c) contacting the organosilicate glass dielectric film with acomposition at a concentration and for a time period effective torestore at least a portion of previously existing carbon containingmoieties or increase the hydrophobicity of the organosilicate glassdielectric film, wherein the composition comprises a component capableof alkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation; an activating agent; and a solvent whichcomprises (i) or (ii):

-   -   (i) a mixture of a main solvent and a co-solvent, which mixture        is capable of solubilizing the component capable of alkylating        or arylating silanol moieties of the organosilicate glass        dielectric film via silylation and the activating agent; which        co-solvent has a higher vapor pressure and/or boiling point than        the main solvent;    -   (ii) ethylacetoacetate, methyl acetoacetate, t-butyl        acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,        benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl        acetate, phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl        acetate, alpha-methylbenzyl acetate, dimethylsulfoxide,        N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,        N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,        N,N-diethylacetamide, N,N-diphenylacetamide,        N,N-dimethypropionamide, N,N-dimethylisobutyramide, 1-hexanol,        2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,        1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,        6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or        combinations thereof.

The invention further provides a method for forming a microelectronicdevice which comprises:

a) forming an organosilicate glass dielectric film on a substrate;

b) forming a pattern of vias and/or trenches in the organosilicate glassdielectric film, and subjecting the organosilicate glass dielectric filmto at least one treatment which removes at least a portion of previouslyexisting carbon containing moieties or reduces hydrophobicity of saidorganosilicate glass dielectric film; and thereafter

c) contacting the organosilicate glass dielectric film with acomposition at a concentration and for a time period effective torestore at least a portion of previously existing carbon containingmoieties or increase the hydrophobicity of the organosilicate glassdielectric film, wherein the composition comprises a component capableof alkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation; an activating agent; and a solvent whichcomprises (i) or (ii):

-   -   (i) a mixture of a main solvent and a co-solvent, which mixture        is capable of solubilizing the component capable of alkylating        or arylating silanol moieties of the organosilicate glass        dielectric film via silylation and the activating agent; which        co-solvent has a higher vapor pressure and/or boiling point than        the main solvent;    -   (ii) ethylacetoacetate, methyl acetoacetate, t-butyl        acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,        benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl        acetate, phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl        acetate, alpha-methylbenzyl acetate, dimethylsulfoxide,        N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,        N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,        N,N-diethylacetamide, N,N-diphenylacetamide,        N,N-dimethypropionamide, N,N-dimethylisobutyramide, 1-hexanol,        2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,        1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,        6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or        combinations thereof.

DETAILED DESCRIPTION OF THE INVENTION

In the context of the present invention, dielectric materials having lowdielectric constants, typically below 3 are especially desirable becausethey typically allow faster signal propagation, reduce capacitiveeffects and cross talk between conductor lines, and lower voltages todrive integrated circuits. This invention relates to both porous andnon-porous dielectric materials. One material with a low dielectricconstant is silica which can be applied as a foamed dielectric material.For the lowest possible dielectric values, air is introduced into silicadielectric materials. Air has a dielectric constant of 1, and when airis introduced into a silica dielectric material in the form ofnanoporous or nanometer-scale pore structures, relatively low dielectricconstants (“k”) are achieved. It should be understood that unless the“SiO₂” functional group is specifically mentioned when the term “silica”is employed, the term “silica” as used herein, for example, withreference to porous and non-porous dielectric films, is intended torefer to dielectric films prepared by the inventive methods from anorganic or inorganic glass base material, e.g., any suitable startingmaterial containing one or more silicon-based dielectric precursors. Itshould also be understood that the use of singular terms herein is notintended to be so limited, but, where appropriate, also encompasses theplural, e.g., exemplary processes of the invention may be described asapplying to and producing a “film” but it is intended that multiplefilms can be produced by the described, exemplified and claimedprocesses, as desired. The term, “film” as used herein with regard tosilica dielectric materials is intended to encompass any other suitableform or shape in which such silica dielectric materials are optionallyemployed. Nanoporous silica is attractive because it employs similarprecursors, including organic-substituted silanes, e.g.,tetramethoxysilane (“TMOS”) and/or tetraethoxysilane (“TEOS”), as areused for the currently employed spin-on-glasses (“SOG”) and chemicalvapor disposition (“CVD”) silica SiO₂. As used herein, the terms “void”and “pore” mean a free volume in which a mass is replaced with a gas orwhere a vacuum is generated. The composition of the gas is generally notcritical, and appropriate gases include relatively pure gases andmixtures thereof, including air. The nanoporous polymer may comprise aplurality of pores. Pores are typically spherical, but may alternativelyor additionally have any suitable shape, including tubular, lamellar,discoidal, or other shapes. The pores may be uniformly or randomlydispersed within the porous polymer. It is also contemplated that thepores may have any appropriate diameter. It is further contemplated thatat least some pores may connect with adjacent pores to create astructure with a significant amount of connected or “open” porosity.

Nanoporous silica films have previously been fabricated by a number ofmethods. Suitable silicon-based precursor compositions and methods forforming nanoporous silica dielectric films, are described, for example,by the following co-owned U.S. Pat. Nos. 6,048,804, 6,022,812;6,410,149; 6,372,666; 6,509,259; 6,218,497; 6,143,855, 6,037,275;6,042,994; 6,048,804; 6,090,448; 6,126,733; 6,140,254; 6,204,202;6,208,041; 6,318,124 and 6,319,855 all incorporated herein by referenceherein.

Other dielectric and low dielectric materials comprise inorganic-basedcompounds, such as the silicon-based disclosed in commonly assignedpending U.S. patent application Ser. No. 10/078,919 filed Feb. 19, 2002;(for example NANOGLASS® and HOSP® products commercially available fromHoneywell International Inc.). The dielectric and low dielectricmaterials may be applied by spin coating the material on to the surface,dip coating, spray coating, chemical vapor deposition (CVD), rolling thematerial onto the surface, dripping the material on to the surface,and/or spreading the material onto the surface. Dielectrics useful forthis invention include CVD deposited materials, such as carbon dopedoxides for example, Black Diamond, commercially available from AppliedMaterials, Inc., Coral, commercially available from Novellus, Aurora,which is commercially available from ASM, and Orion, which iscommercially available from Trikon.

As used herein, the phrases “spin-on material”, “spin-on organicmaterial”, “spin-on composition” and “spin-on inorganic composition” maybe used interchangeable and refer to those solutions and compositionsthat can be spun-on to a substrate or surface using the spin coatingapplication process. Examples of silicon-based compounds comprisesiloxane compounds, such as methylsiloxane, methylsilsesquioxane,phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane,methylphenylsilsesquioxane, silazane polymers, silicate polymers andmixtures thereof. A contemplated silazane polymer is perhydrosilazane,which has a “transparent” polymer backbone where chromophores can beattached. Spin-on-glass materials also includes siloxane polymers andblock polymers, hydrogensiloxane polymers of the general formula(H_(0-1.0)SiO_(1.5-2.0))_(x) and hydrogensilsesquioxane polymers, whichhave the formula (HSiO_(1.5))_(x), where x is greater than about four.Also included are copolymers of hydrogensilsesquioxane and analkoxyhydridosiloxane or hydroxyhydridosiloxane. Spin-on glass materialsadditionally include organohydridosiloxane polymers of the generalformula (H_(0-1.0)Si_(0.5-2.0))_(n)(R_(0-1.0)SiO_(1.5-2.0))_(m), andorganohydridosilsesquioxane polymers of the general formula(HSiO_(1.5))_(n)(RSiO_(1.5))_(m), where m is greater than zero and thesum of n and m is greater than about four and R is alkyl or aryl. Someuseful organohydridosiloxane polymers have the sum of n and m from aboutfour to about 5000 where R is a C₁-C₂₀ alkyl group or a C₆-C₁₂ arylgroup. The organohydridosiloxane and organohydridosilsesquioxanepolymers are alternatively denoted spin-on-polymers. Some specificexamples include alkylhydridosiloxanes, such as methylhydridosiloxanes,ethylhydridosiloxanes, propylhydridosiloxanes, t-butylhydridosiloxanes,phenylhydridosiloxanes; and alkylhydridosilsesquioxanes, such asmethylhydridosilsesquioxanes, ethylhydridosilsesquioxanes,propylhydridosilsesquioxanes, t-butylhydridosilsequioxanes,phenylhydridosilsesquioxanes, and combinations thereof. Several of thecontemplated spin-on materials are described in the following issuedpatents and pending applications, which are herein incorporated byreference in their entirety: U.S. Pat. Nos. 6,506,497; 6,365,765;6,268,457; 6,177,199; 6,358,559; 6,218,020; 6,361,820; 6,218,497;6,359,099; 6,143,855; 6,512,071, U.S. patent application Ser. No.10/001,143 filed Nov. 10, 2001; PCT/US00/15772 filed Jun. 8, 2000, andPCT/US00/00523 filed Jan. 7, 1999.

Solutions of organohydridosiloxane and organosiloxane resins can beutilized for forming caged siloxane polymer films that are useful in thefabrication of a variety of electronic devices, micro-electronicdevices, particularly semiconductor integrated circuits and variouslayered materials for electronic and semiconductor components, includinghard mask layers, dielectric layers, etch stop layers and buried etchstop layers. These organohydridosiloxane resin layers are compatiblewith other materials that might be used for layered materials anddevices, such as adamantane-based compounds, diamantane-based compounds,silicon-core compounds, organic dielectrics, and nanoporous dielectrics.Compounds that are considerably compatible with theorganohydridosiloxane resin layers contemplated herein are disclosed inU.S. Pat. Nos. 6,214,746; 6,171,687; 6,172,128; 6,156,812, U.S.application Ser. No. 60/350187 filed Jan. 15, 2002; U.S. patentapplication Ser. No. 09/538,276; U.S. patent application Ser. No.09/54,4504; U.S. patent application Ser. No. 09/587,851; and U.S.60/347195 filed Jan. 8, 2002; PCT Application PCT/US01/32569 filed Oct.17, 2001; PCT Application PCT/US01/50812 filed Dec. 31, 2001, which areall incorporated herein by reference.

Suitable organohydridosiloxane resins utilized herein have the followinggeneral formulas:[H—Si_(1.5)]_(n)[R—SiO_(1.5)]_(m)   Formula (1)[H_(0.5)—Si_(1.5-1.8)]_(n)[R_(0.5-1.0)—SiO_(1.5-1.8)]_(m)   Formula (2)[H_(0-1.0)—Si_(1.5)]_(n)[R—SiO_(1.5)]_(m)   Formula (3)[H—Si_(1.5)]_(x)[R—SiO_(1.5)]_(y)[SiO₂]_(z)   Formula (4)wherein:

the sum of n and m, or the sum or x, y and z is from about 8 to about5000, and m or y is selected such that carbon containing constituentsare present in either an amount of less than about 40 percent (LowOrganic Content=LOSP) or in an amount greater than about 40 percent(High Organic Content=HOSP); R is selected from substituted andunsubstituted, normal and branched alkyls (methyl, ethyl, butyl, propyl,pentyl), alkenyl groups (vinyl, allyl, isopropenyl), cycloalkyls,cycloalkenyl groups, aryls (phenyl groups, benzyl groups, naphthalenylgroups, anthracenyl groups and phenanthrenyl groups), and mixturesthereof, and wherein the specific mole percent of carbon containingsubstituents is a function of the ratio of the amounts of startingmaterials. In some LOSP embodiments, particularly favorable results areobtained with the mole percent of carbon containing substituents beingin the range of between about 15 mole percent to about 25 mole percent.In some HOSP embodiments, favorable results are obtained with the molepercent of carbon containing substituents are in the range of betweenabout 55 mole percent to about 75 mole percent.

Nanoporous silica dielectric films with dielectric constants rangingfrom about 1.5 to about 4 can also be used as one of the layers.Nanoporous silica films are laid down as a silicon-based precursor, agedor condensed in the presence of water and heated sufficiently to removesubstantially all of the porogen and to form voids in the film. Thesilicon-based precursor composition comprises monomers or prepolymersthat have the formula: R_(x)—Si-L_(y), wherein R is independentlyselected from alkyl groups, aryl groups, hydrogen and combinationsthereof, L is an electronegative moiety, such as alkoxy, carboxy, amino,amido, halide, isocyanato and combinations thereof, x is an integerranging from 0 to about 2, and y is an integer ranging from about 2 toabout 4. Other nanoporous compounds and methods can be found in U.S.Pat. Nos. 6,171,687; 6,172,128; 6,214,746; 6,313,185; 6,380,347; and6,380,270, which are incorporated herein in their entirety.

The phrases “cage structure”, “cage molecule”, and “cage compound” areintended to be used interchangeably and refer to a molecule having atleast 10 atoms arranged such that at least one bridge covalentlyconnects two or more atoms of a ring system. In other words, a cagestructure, cage molecule or cage compound comprises a plurality of ringsformed by covalently bound atoms, wherein the structure, molecule orcompound defines a volume, such that a point located with the volume cannot leave the volume without passing through the ring. The bridge and/orthe ring system may comprise one or more heteroatoms, and may bearomatic, partially saturated, or unsaturated. Further contemplated cagestructures include fullerenes, and crown ethers having at least onebridge. For example, an adamantane or diamantane is considered a cagestructure, while a naphthalene compound or an aromatic spiro compoundare not considered a cage structure under the scope of this definition,because a naphthalene compound or an aromatic spiro compound do not haveone, or more than one bridge. Contemplated cage compounds need notnecessarily be limited to being comprised solely of carbon atoms, butmay also include heteroatoms such as N, S, O, P, etc. Heteroatoms mayadvantageously introduce non-tetragonal bond angle configurations. Withrespect to substituents and derivatizations of contemplated cagecompounds, it should be recognized that many substituents andderivatizations are appropriate. For example, where the cage compoundsare relatively hydrophobic, hydrophilic substituents may be introducedto increase solubility in hydrophilic solvents, or vice versa.Alternatively, in cases where polarity is desired, polar side groups maybe added to the cage compound. It is further contemplated thatappropriate substituents may also include thermolabile groups,nucleophilic and electrophilic groups. It should also be appreciatedthat functional groups may be utilized in the cage compound (e.g., tofacilitate crosslinking reactions, derivatization reactions, etc.) Cagemolecules or compounds, as described in detail herein, can also begroups that are attached to a polymer backbone, and therefore, can formnanoporous materials where the cage compound forms one type of void(intramolecular) and where the crosslinking of at least one part of thebackbone with itself or another backbone can form another type of void(intermolecular). Additional cage molecules, cage compounds andvariations of these molecules and compounds are described in detail inPCT/US01/32569 filed on Oct. 18, 2001, which is herein incorporated byreference in its entirety. Contemplated polymers may also comprise awide range of functional or structural moieties, including aromaticsystems, and halogenated groups. Furthermore, appropriate polymers mayhave many configurations, including a homopolymer, and a heteropolymer.Moreover, alternative polymers may have various forms, such as linear,branched, super-branched, or three-dimensional. The molecular weight ofcontemplated polymers spans a wide range, typically between 400 Daltonand 400000 Dalton or more. Additives can also be used to enhance orimpart particular properties, as is conventionally known in the polymerart, including stabilizers, flame retardants, pigments, plasticizers,surfactants, and the like. Compatible or non-compatible polymers can beblended in to give a desired property. Adhesion promoters can also beused. Such promoters are typified by hexamethyldisilazane, which can beused to interact with available hydroxyl functionality that may bepresent on a surface, such as silicon dioxide, that was exposed tomoisture or humidity. Polymers for microelectronic applicationsdesirably contain low levels (generally less than 1 ppm, preferably lessthan 10 ppb) of ionic impurities, particularly for dielectricinterlayers.

The materials, precursors and layers described herein can be and in manyways are designed to be solvated or dissolved in any suitable solvent,so long as the resulting solutions can be applied to a substrate, asurface, a wafer or layered material. Typical solvents are also thosesolvents that are able to solvate the monomers, isomeric monomermixtures and polymers. Contemplated solvents include any suitable pureor mixture of organic or inorganic molecules that are volatilized at adesired temperature, such as the critical temperature, or that canfacilitate any of the above-mentioned design goals or needs. The solventmay also comprise any suitable single polar and non-polar compounds ormixture thereof. As used herein, the term “polar” means thatcharacteristic of a molecule or compound that creates an unequal charge,partial charge or spontaneous charge distribution at one point of oralong the molecule or compound. As used herein, the term “non-polar”means that characteristic of a molecule or compound that creates anequal charge, partial charge or spontaneous charge distribution at onepoint of or along the molecule or compound. In some contemplatedembodiments, the solvent or solvent mixture (comprising at least twosolvents) comprises those solvents that are considered part of thehydrocarbon family of solvents. Hydrocarbon solvents are those solventsthat comprise carbon and hydrogen. It should be understood that amajority of hydrocarbon solvents are non-polar; however, there are a fewhydrocarbon solvents that could be considered polar. Hydrocarbonsolvents are generally broken down into three classes: aliphatic, cyclicand aromatic. Aliphatic hydrocarbon solvents may comprise bothstraight-chain compounds and compounds that are branched and possiblycrosslinked, however, aliphatic hydrocarbon solvents are not consideredcyclic. Cyclic hydrocarbon solvents are those solvents that comprise atleast three carbon atoms oriented in a ring structure with propertiessimilar to aliphatic hydrocarbon solvents. Aromatic hydrocarbon solventsare those solvents that comprise generally three or more unsaturatedbonds with a single ring or multiple rings attached by a common bondand/or multiple rings fused together. Contemplated hydrocarbon solventsinclude toluene, xylene, p-xylene, m-xylene, mesitylene, solvent naphthaH, solvent naphtha A, alkanes, such as pentane, hexane, isohexane,heptane, nonane, octane, dodecane, 2-methylbutane, hexadecane,tridecane, pentadecane, cyclopentane, 2,2,4-trimethylpentane, petroleumethers, halogenated hydrocarbons, such as chlorinated hydrocarbons,nitrated hydrocarbons, benzene, 1,2-dimethylbenzene,1,2,4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene,methylnaphthalene, ethyltoluene, ligroine. Particularly contemplatedsolvents include, but are not limited to, pentane, hexane, heptane,cyclohexane, benzene, toluene, xylene and mixtures or combinationsthereof.

In other contemplated embodiments, the solvent or solvent mixture maycomprise those solvents that are not considered part of the hydrocarbonsolvent family of compounds, such as ketones, such as acetone,3-pentanone, diethyl ketone, methyl ethyl ketone and the like, alcohols,ketones, esters, ethers and amines. In yet other contemplatedembodiments, the solvent or solvent mixture may comprise a combinationof any of the solvents mentioned herein. In some embodiments, thesolvent comprises water, ethanol, propanol, acetone, ethylene oxide,benzene, toluene, ethers, cyclohexanone, butyrolactone,methylethylketone, and anisole.

It is still further contemplated that alternative low dielectricconstant material may also comprise additional components. For example,where the low dielectric constant material is exposed to mechanicalstress, softeners or other protective agents may be added. In othercases where the dielectric material is placed on a smooth surface,adhesion promoters may advantageously employed. In still other cases,the addition of detergents or antifoam agents may be desirable. Ingeneral, a precursor in the form of, e.g., a spin-on-glass compositionthat includes one or more removable solvents, is applied to a substrate,and then polymerized and subjected to solvent removal in such a way asto form a dielectric film comprising nanometer-scale pores.

When forming such nanoporous films, e.g., wherein the precursor isapplied to a substrate by spin-coating, the film coating is typicallycatalyzed with an acid or base catalyst and water to causepolymerization/gelation (“aging”) during an initial heating step. Thefilm is then cured, e.g., by subjecting the film to one or more highertemperature heating steps to, inter alia, remove any remaining solventand complete the polymerization process, as needed. Other curing methodsinclude subjecting the film to radiant energy, e.g., ultraviolet,electron beam, microwave energy, and the like.

Co-owned U.S. Pat. Nos. 6,204,202 and 6,413,882, incorporated byreference herein, provide silicon-based precursor compositions andmethods for forming nanoporous silica dielectric films by degrading orvaporizing one or more polymers or oligomers present in the precursorcomposition. Co-owned U.S. Pat. No. 6,495,479, provides silicon-basedprecursor compositions and methods for forming nanoporous silicadielectric films by degrading or vaporizing one or more compounds orpolymers present in the precursor composition. U.S. Pat. No. 5,895,263describes forming a nanoporous silica dielectric film on a substrate,e.g., a wafer, by applying a composition comprising decomposable polymerand organic polysilica i.e., including condensed or polymerized siliconpolymer, heating the composition to further condense the polysilica, anddecomposing the decomposable polymer to form a porous dielectric layer.

Processes for application of precursor to a substrate, aging, curing,planarization, and rendering the film(s) hydrophobic are described, forexample, by co-owned U.S. Pat. Nos. 6,589,889 and 6,037,275, amongothers. Substrates and wafers contemplated herein may comprise anydesirable substantially solid material. Particularly desirable substratelayers would comprise films, glass, ceramic, plastic, metal or coatedmetal, or composite material. In preferred embodiments, the substratecomprises a silicon or germanium arsenide die or wafer surface, apackaging surface such as found in a copper, silver, nickel or goldplated leadframe, a copper surface such as found in a circuit board orpackage interconnect trace, a via-wall or stiffener interface (“copper”includes considerations of bare copper and it's oxides), a polymer-basedpackaging or board interface such as found in a polyimide-based flexpackage, lead or other metal alloy solder ball surface, glass andpolymers such as polyimide. The “substrate” may even be defined asanother polymer chain when considering cohesive interfaces. In morepreferred embodiments, the substrate comprises a material common in thepackaging and circuit board industries such as silicon, copper, glass,and another polymer.

Subsequent semiconductor manufacturing processes such as deposition ofcap film by PECVD techniques, and via and trench formation by patterningby means of etching and ashing, atomic layer deposition, physical vapordeposition, and a chemical vapor deposition treatment tend to removecarbon containing moieties which are hydrophobic groups from theorganosilicate glass dielectric films and replace them with silanolgroups. Undesirable properties result when the organosilicate glassdielectric films contain silanol groups. Silanols, and the water thatthey can adsorb from the air are highly polarizable in an electricfield, and thus will raise the dielectric constant of the film, and willlower resistance to wet cleaning chemistries and increase volatileevolution. Also, when the trenches and vias are filled with a metal andsubjected to an annealing treatment, metal shrinkage induces a stress onthe via and trench walls and cause undesirable voids to form inside thedielectric material between the vias and/or trenches.

In order to remedy this problem, the organosilicate glass dielectricfilms are made substantially free of silanols and water by treatmentwith a treating agent to restore carbon containing moieties and increasethe hydrophobicity of the organosilicate glass dielectric film. Thismakes the film resistant to stresses on the via and trench walls, suchas induced by metal shrinkage during annealing, stress from otherdielectric layers, and stress during packaging, thus deters undesirablevoids from forming inside the dielectric material between the viasand/or trenches.

Etching and plasma remove hydrophobic functional groups. Damage toorganosilicate glass dielectric films during semiconductor manufacturingprocesses results from the application of aggressive plasmas and/oretching reagents to etch trenches and vias into dielectric films.Plasmas are also used to remove photoresist films during fabrication ofsemiconductor devices. The plasmas used are typically composed of theelements oxygen, fluorine, hydrogen, carbon, argon, helium or nitrogen(in the form of free atoms, compounds, ions and/or radicals).

Dielectric films which are exposed to these plasmas during trench, via,etch and/or photoresist removal are easily degraded or damaged. Porousdielectric films have a very high surface area and are thereforeparticularly vulnerable to plasmas damage. In particular, silica baseddielectric films which have organic content (such as methyl groupsbonded to Si atoms) are readily degraded by oxygen plasmas. The organicgroup is oxidized into CO₂ and a silanol or Si—OH group remains on thedielectric surface where the organic group formerly resided. Porous andnon-porous low dielectric constant silica films depend on such organicgroups (on surfaces) to remain hydrophobic. Loss of the hydrophobicitymakes the dielectric constant rise (the low dielectric constant of suchfilms is the key desired property of such materials).

Wet chemical treatments are also used in IC production for the purposeof removing residues leftover after trench or via etching. The chemicalsused are often so aggressive they will attack and remove organic groupsin silica based dielectric films, especially porous silica films. Again,this damage will cause the films to lose their hydrophobicity. Wetchemical etchants include, for example, amides, such asN-methylpyrrolidinone, dimethylformamide, dimethylacetamide; alcoholssuch as ethanol and 2-propanol; alcoholamines such as ethanolamine;amines such as triethylamine; diamines such as ethylenediamine andN,N-diethylethylenediamine; triamines such as diethylenetriamine,diamine acids such as ethylenediaminetetracetic acid “EDTA”; organicacids such as acetic acid and formic acid; the ammonium salts of organicacids such as tetramethylammonium acetate; inorganic acids such assulfuric acid, phosphoric acid, hydrofluoric acid; fluoride salts suchas ammonium fluoride; and bases such as ammonium hydroxide andtetramethyl ammonium hydroxide; and hydroxyl amine; commercialformulations developed for post etch wet cleaning such as EKC 505, 525,450, 265, 270, and 630 (EKC Corp., Hayward Calif.), and ACT-CMI andACT-690 (Ashland Chemical, Hayward, Calif.). to name but a few art-knownetchants. Ashing agents include plasmas derived from hydrogen, nitrogen,helium, argon, oxygen, and mixtures derived therefrom, and the like.

In order to solve the above mentioned problems the invention providesmethods of imparting hydrophobic properties to organosilicate glassdielectric films present on a substrate during the process offabricating a semiconductor or IC device.

The methods of the invention include the steps of contacting theorganosilicate glass dielectric film, after being subjected to at leastone etchant or ashing reagent, but before said metal has been subjectedto an annealing treatment, with a treating agent composition at aconcentration and for a time period effective to restore at least someof the carbon containing moieties to the organosilicate glass dielectricfilm and increase the hydrophobicity of the organosilicate glassdielectric film; and (b) removing unreacted treating agent composition,reaction products and mixtures thereof. The treating agent compositionincludes at least one treating agent, i.e., a compound or chargedderivative thereof, suitable for removing silanol moieties from thedamaged silica dielectric film. Optionally, the etchant-damaged silicadielectric film is then subjected to wet cleaning step.

The overall treating agent composition comprises a component capable ofalkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation, an activating agent which may be anacid, a base, an onium compound, a dehydrating agent, and combinationsthereof; and a selected solvent, or mixture of a main solvent and aco-solvent capable of solubilizing with the component capable ofalkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation, and the activating agent.

A suitable treating agent composition includes one or more treatingagents able to remove silanol groups from the surface of an etchedand/or ashed organosilicate glass dielectric film that it is desired torender hydrophobic. These may be silane, silazane, silanols, orcarboxysilyl. For example, a treating agent is a compound having aFormula:

1 (1-13): (1) [—SiR₂NR′—]n where n>2 and may be cyclic; (2) R₃SiNR′SiR₃,(3) (R₃Si)₃N; (4) R₃SiNR′₂; (5) R₂Si(NR′)₂; (6) RSi(NR′)₃; (7)R_(x)SiCl_(y), (8) R_(x)Si(OH)_(y), (9) R₃SiOSiR′₃, (10)R_(x)Si(OR′)_(y), (11) R_(x)Si(OCOR′)_(y), (12) R_(x)SiH_(y); (13)R_(x)Si[OC(R′)═R″]_(4-x) or combinations thereof,

wherein x is an integer ranging from 1 to 3, y is an integer rangingfrom 1 to 3 such that y=4-x; each R is an independently selected fromhydrogen and a hydrophobic organic moiety. The R groups are preferablyindependently organic moieties consisting of alkyl, aryl andcombinations thereof. The R′ group may be H, alkyl, aryl, or carbonylsuch as COR, CONR, CO₂R. The R″ may be alkyl or carbonyl such as COR,CONR, CO₂R

For all treating agents, the reactive silyl group must contain ahydrolyzable leaving group such as but not limited to —Cl, —Br, —I, —OR,—NR_(x) (where x=1-2), —OCOR, —OCO₂R, —NRCOR, —NRCO₂R, —NRCONR, —SR,—SO₂R. For reaction of the treating agent, hydrolysis may occurspontaneously with moisture present during the treating agentapplication and process, or pre-hydrolysis may be forced during theformulation process.

The alkyl moiety is either functionalized or non-functionalized and isderived from groups of straight alkyl, branched alkyl, cyclic alkyl andcombinations thereof, and wherein said alkyl moiety ranges in size fromC₁ to about C₁₈. The functionalization may be a carbonyl, a halide, anamine, an alcohol, an ether, a sulfonyl or sulfide. The aryl moiety issubstituted or unsubstituted and ranges in size from C₅ to about C₁₈Preferably the treating agent is an acetoxysilane, or, for example, amonomer compound such as acetoxysilane, diacetoxysilane,triacetoxysilane, acetoxytrimethylsilane, diacetoxydimethylsilane,methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane,methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane,methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane,methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorsilane,methylsilane, dimethylsilane, trimethylsilane, hexamethyldisilazane,hexamethylcyclotrisilazane, bis(dimethylamino)dimethylsilane,bis(diethylamino)dimethylsilane, tris(dimethylamino)methylsilane,tris(dimethylamino)phenylsilane, tris(dimethylamino)silane,dimethylsilyldiformamide, dimethylsilyldiacetamide,dimethylsilyldiisocyante, trimethylsilyltriisocyanate,2-trimethylsiloxypent-2-ene-4-one, n-(trimethylsilyl)acetamide,2-(trimethylsilyl) acetic acid, n-(trimethylsilyl)imidazole,trimethylsilylpropiolate, trimethylsilyl(trimethylsiloxy)-acetate,nonamethyltrisilazane, hexamethyldisiloxane, trimethylsilanol,triethylsilanol, triphenylsilanol, t-butyldimethylsilanol,diphenylsilanediol, trimethoxysilane, triethoxysilane, trichlorosilane,and combinations thereof. In one noteworthy embodiment, the treatingagent is methyltriacetoxysilane. In a preferred embodiment the treatingagent is dimethyldiacetoxysilane.

Additional treating agents include multifunctional surface modificationagents as described in detail in U.S. Pat. No. 6,208,014, incorporatedby reference herein, as described above. Such multifunctional surfacemodification agents can be applied in either vapor or liquid form,optionally with or without co-solvents.

For example, as described in detail in U.S. Pat. No. 6,208,014, certainpreferred surface modification agents will have two or more functionalgroups and react with surface silanol functional groups while minimizingmass present outside the structural framework of the film, and include,e.g., surface silanols may condense with suitable silanols such asR_(x)Si(OH₂)_(4-x)

Wherein x=1-3, and each R is independently selected moieties, such as Hand/or an organic moiety such as an alkyl, aryl or derivatives of these.When R is an alkyl, the alkyl moiety is optionally substituted orunsubstituted, and may be straight, branched or cyclic, and preferablyranges in size from C₁ to about C₁₈, or greater, and more preferablyfrom C₁ to about C₈. When R is aryl, the aryl moiety preferably consistsof a single aromatic ring that is optionally substituted orunsubstituted, and ranges in size from C₅ to about C₁₈, or greater, andmore preferably from C₅ to about C₈. In a further option, the arylmoiety is a heteroaryl.

In another embodiment, alkoxy silanes may be used as the treating agent,e.g. suitable alkoxy silanes such asR_(x)Si(OR′)_(4-x)

wherein R are independently selected moieties, such as H and/or anorganic moiety such as an alkyl, aryl or derivatives of these; R′ areindependently selected alkyl or aryl moieties. When R or R′ is an alkyl,the alkyl moiety is optionally substituted or unsubstituted, and may bestraight, branched or cyclic, and preferably ranges in size from C₁ toabout C₁₈, or greater, and more preferably from C₁ to about C₈. When Ror R′ is aryl, the aryl moiety preferably consists of a single aromaticring that is optionally substituted or unsubstituted, and ranges in sizefrom C₅ to about C₁₈, or greater, and more preferably from C₅ to aboutC₈. In a further option, the aryl moiety is a heteroaryl. Thus, the Rgroups independently selected from H, methyl, ethyl, propyl, phenyl,and/or derivatives thereof, provided that at least one R is organic. Inone embodiment, both R groups are methyl, and a tri-functional surfacemodification agent is methyltrimethoxysilane. In another embodiment, asuitable silane according to the invention has the general formula ofR_(X)Si(NR₂)_(4-x)

wherein X=1-3, R are independently H, alkyl and/or aryl. When any R arealkyl and/or aryl. In preferred embodiments, R is selected from H, CH₃,C₆H₅, and R₂ and R₃ are both CH₃. Thus tri-functional treating agentsinclude, e.g., tris(dimethylamino)methylsilane,tris(dimethylamino)phenylsilane, and/or tris(dimethylamino)silane. Inaddition, disubstituted silanes may be used such ashexamethylcyclotrisilazane, bisdimethylaminodimethylsilane, andbisdiethylaminodimethylsilane.

In yet another embodiment, a suitable silane according to the inventionhas the general formula ofR_(x)Si(ON═CR₂)_(4-x) or R_(x)Si[OC(R′)═R″]_(4-x)

wherein x=1-3 and the R groups are independently H, alkyl and/or aryl,R′ may be H, alkyl, aryl, alkoxy or aryloxy, and R″ may be alkyl orcarbonyl. Thus modification agents include, e.g.,methyltris(methylethylketoxime)silane or2-trimethylsiloxypent-2-ene-4-one respectively.

In yet another embodiment, a suitable silane according to the inventionhas the general formula ofR_(x)Si(NCOR₂)_(4-x) or R_(x)Si(NCO)_(4-x)

wherein x=1-3, R groups are independently H, alkyl and/or aryl. Thussurface modification agents include, e.g., dimethylsilyldiformamide,dimethylsilyldiacetamide, dimethylsilyldiisocyante,trimethylsilyltriisocyante.

In yet a further embodiment, a suitable silane according to theinvention has the general formula ofR_(x)SiCl_(4-x)

wherein x=1-3, is H, alkyl or aryl. In one preferred embodiment, R_(x)is CH₃. Thus tri-functional surface modification agents include, e.g.,methyltrichlorosilane.

In a more preferred embodiment, the treating agent includes one or moreorganoacetoxysilanes which have the following general formula,(R₁)_(x)Si(OCOR₂)_(y)

Preferably, x is an integer ranging in value from 1 to 2, and x and ycan be the same or different and y is an integer ranging from about 2 toabout 3, or greater.

Useful organoacetoxysilanes, including multifunctionalalkylacetoxysilane and/or arylacetoxysilane compounds, include, simplyby way of example and without limitation, methyltriacetoxysilane(“MTAS”), dimethyldiacetoxysilane (DMDAS), phenyltriacetoxysilane anddiphenyldiacetoxysilane and combinations thereof.

The component capable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation is usually presentin the treating agent composition in an amount of from about 0.1 weightpercent to about 100 weight percent, more usually from about 1 weightpercent to about 50 weight percent, and most usually from about 3 weightpercent to about 30 weight percent.

The treating agent composition then contains an activating agent may bean activating agent which may be an acid, a base, an onium compound, adehydrating agent, or combinations thereof. Useful activating agentsinclude amines, ammonium compounds, phosphonium compounds, sulfoniumcompounds, iodonium compounds, hydroxides, alkoxides, acid halides,silanolates, amine salts, and combinations thereof. Included areactivating agents which may be alkyl amines, aryl amines, alcohol aminesand mixtures thereof which suitably have a boiling point of about 100°C. or higher, usually about 125° C. or higher and more usually about150° C. or higher. Useful acid activating agents non-exclusively includehydrochloric acid, sulfuric acid, nitric acid, boric acid, ethylsulfuricacid, chlorosulfuric acid, phosphonitrile chloride, iron chloride, zincchloride, tin chloride, aluminum chloride, boron trifluoride,methanesulfonic acid, trifluoromethanesulfonic acid, iron chloridehexahydrate or combinations thereof. Useful activating agents which aredehydrating agents non-exclusively include phosphorous halides,phosphorous pentoxide, phenylphosphonic dichloride, and phenylphosphorodichloridate, and combinations thereof.

Useful amine activating agent include primary amines, secondary amines,tertiary amines, ammonia, and quaternary ammonium salts. Useful aminesare monoethanolamine, diethanolamine, triethanolamine,monoisopropanolamine, tetraethylenepentamine, 2-(2-aminoethoxy)ethanol;2-(2-aminoethylamino)ethanol and mixtures thereof.

In a desired embodiment of the invention the activating agent comprisestetramethylammonium acetate, tetrabutylammonium acetate or combinationsthereof. Other activating agents include sodium hydroxide, cesiumhydroxide, potassium hydroxide, lithium hydroxide and ammoniumhydroxide. The activating agent is usually present in the treating agentcomposition in an amount of from about 0.0001 weight percent to about 10weight percent, more usually from about 0.001 weight percent to about 1weight percent, and most usually from about 0.01 weight percent to about0.1 weight percent.

The treating agent composition includes a solvent capable ofsolubilizing with the component capable of alkylating or arylatingsilanol moieties of the organosilicate glass dielectric film viasilylation, and the activating agent.

In one embodiment, the solvent comprises a miscible mixture of a mainsolvent and a co-solvent, which mixture is capable of solubilizing thecomponent capable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation and the activatingagent; and which co-solvent has a higher vapor pressure and/or boilingpoint than the main solvent. In one embodiment, the main solvent has aboiling point of from about 100° C. to about 300° C., preferably fromabout 110° C. to about 250° C., and more preferably from about 130° C.to about 180° C. In an embodiment, the co-solvent has a boiling point offrom about 1° C. to about 100° C. higher than the main solvent. Inanother embodiment, the co-solvent has a boiling point of from about 10°C. to about 70° C. higher than the main solvent. In another embodiment,the co-solvent has a boiling point of from about 20° C. to about 50° C.higher than the main solvent.

The main solvent may be one or more ketones, ethers, esters,hydrocarbons, alcohols, carboxylic acids, amines, amides, andcombinations thereof. Useful main solvents non-exclusively include3-pentanone, 2-heptanone, gammabutyrolactone, propylene glycol methylether acetate, acetic acid, and combinations thereof.

Co-solvents may be ethylacetoacetate, methyl acetoacetate, t-butylacetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzylacetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthylacetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzylacetate, dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1,2-dichlorobenzene, chlorotoluene,1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or combinationsthereof. Preferably the co-solvent comprises ethylacetoacetate,dimethylsulfoxide, 1-hexanol, or combinations thereof. Preferably themain solvent is present in the mixture in an amount of from about 0.1 toabout 99.9 percent by weight of the miscible mixture, more preferablyfrom about 50 to about 99 percent by weight of the miscible mixture, andstill more preferably from about 70 to about 97 percent by weight of themiscible mixture. Preferably the co-solvent is present in the mixture inan amount of from about 0.1 to about 99.9 based on the percent by weightof the miscible mixture, more preferably from about 0.5 to about 50percent by weight of the miscible mixture, and still more preferablyfrom about 1 to about 30 percent by weight of the miscible mixture.

In another embodiment of the invention, the above main solvent is notused and the treating composition comprises one or more of theco-solvents listed above.

The total amount of solvent present in the treating agent compositionmay be an amount of from about 0.1 weight percent to about 99.9 weightpercent, more usually from about 50 weight percent to about 99 weightpercent, and most usually from about 70 weight percent to about 97weight percent.

Optionally, the treating agent composition includes a corrosioninhibitor, such as a corrosion inhibitor which chelates with copper.Such may include benzotriazole, tolyltriazole, and combinations thereof.The corrosion inhibitor, when employed, is usually present in thetreating agent composition in an amount of from about 0.001 weightpercent to about 10 weight percent, more usually from about 0.01 weightpercent to about 5 weight percent, and most usually from about 0.2weight percent to about 1 weight percent.

The treating agent composition is formed by blending the selectedcomponents into a mixture. The treating agent composition contacts thedamaged silica dielectric film as a liquid, vapor or gas, and/or plasma.If in the form of a plasma, the plasma can be derived from a silanecompound, a hydrocarbon, an aldehyde, an ester, an ether, and/orcombinations thereof. The terms, “agent” or “agents” herein should beconsidered to be synonymous with the terms, “reagent” or “reagents,”unless otherwise indicated. Optionally the treatment further comprisesthe subsequent step of removing unreacted treating agent composition,reaction products and mixtures thereof and/or the subsequent step ofheating the increased hydrophobicity organosilicate glass dielectricfilm.

In yet another embodiment, a wet clean using chemicals such as AP395 ordilute HF is performed after the bake step in the above-mentionedembodiments. The wet clean is useful to remove any resist residuesremaining after the ash. Untreated low-k dielectric materials after etchand ash are prone to attack by the wet clean agents. The treating agenttreatment significantly improves resistance of the low-k dielectric toattack by wet clean.

Depending on the process flow, a copper surface may be exposed duringthe treating agent treatment, especially at the bottom of via. Inaddition to removing native oxide from copper surface, the wet clean canalso remove any reaction product between treating agent and an exposedcopper surface. Specifically, a wet clean using AP395 can clean a copper(or any suitable metal or metal alloy) surface that is previouslyexposed to a treating agent treatment using DMDAS.

As used herein, the term “metal” means those elements that are in thed-block and f-block of the Periodic Chart of the Elements, along withthose elements that have metal-like properties, such as silicon andgermanium. As used herein, the phrase “d-block” means those elementsthat have electrons filling the 3d, 4d, 5d, and 6d orbitals surroundingthe nucleus of the element. As used herein, the phrase “f-block” meansthose elements that have electrons filling the 4f and 5f orbitalssurrounding the nucleus of the element, including the lanthanides andthe actinides. Preferred metals include indium, silver, copper,aluminum, tin, bismuth, gallium and alloys thereof, silver coatedcopper, and silver coated aluminum. The term “metal” also includesalloys, metal/metal composites, metal ceramic composites, metal polymercomposites, as well as other metal composites.

In yet another embodiment, the wet clean can be performed before thebake process in the first contemplated embodiment. The high temperaturebake step is performed after the wet clean. An advantage of this methodcan be that the wet clean can remove excess treating agent and anyreaction product with any exposed copper surface, before it is“hardened” by the bake process. This can result in lower volatilecomponents in the dielectric material and a cleaner copper surface. Bothcan result in an improved long term reliability.

In another contemplated embodiment, an additional dehydration bake at100-400° C. from 1 min to 120 min is performed before the treating agent(TA) treatment. The dehydration bake removes any moisture adsorbed inthe damaged low-k dielectric. Removal of moisture from the dielectricprior to treating agent treatment renders the treatment more effective.

In an alternative embodiment, the treating agent composition is providedby exposing the etchant-damaged organosilicate glass dielectric film toa plasma which is derived from any of the above mentioned treatingagent. In a typical procedure, the organosilicate glass dielectric filmis placed in a plasma generating chamber, such as a plasma enhancedchemical vapor deposition (PECVD) system; the vapor of a treating agentcomposition and argon vapor are passed through the plasma generatingchamber; then an RF energy source is activated to create a plasma; theargon gas is included to help promote the formation of plasma. Theplasma is composed of ionic fragments derived from the treating agentcomposition; for example, the ion fragment CH₃Si⁺ is generated frommethylsilane (CH₃SiH₃). This fragment reacts with silanol groups to formhydrophobic Si—CH₃ moieties. Any of the above mentioned treating agentcompositions can be used for this plasma induced surface treatment.

Other suitable treating agent compositions for a plasma induced surfacetreatment include C₁-C₁₂ alkyl and aromatic hydrocarbons. The mostpreferred hydrocarbon is methane. Other reagents for plasma inducedtreating agent compositions include aldehydes, esters, acid chlorides,and ethers. Suitable aldehydes include acetaldehyde and benzaldehyde;suitable esters include ethyl acetate and methyl benzoate; suitable acidchlorides include acetyl chloride and benzyl chloride; and suitableethers include diethyl ether and anisole. A wide variety of single waferor multiple wafer (batch) plasma systems can be used for this process;these systems include so called downstream ashers, such as the GasonicsL3510 photoresist asher, PECVD dielectric deposition systems such as theApplied Materials P5000, or reactive ion etch (“RIE”) systems. Broadly,the conditions for the plasma process are within the following ranges:chamber temperature, 20C to 450° C.; RF power, 50 W to 1000 W; chamberpressure, 0.05 to 100 torr; plasma treatment time, 5 seconds to 5minutes; and surface modification flow rate, 100-2000 sccm; inert gasflow rate (typically argon), 100-2000 sccm.

The artisan will appreciate that the invention is also contemplated toencompass methods of imparting a hydrophobic surface to silicadielectric films, porous and/or nonporous, whether damaged or not, byapplication of the above-described plasma surface treatments.Microelectronic devices, such as semiconductor devices or ICsmanufactured using these methods are also a part of the presentinvention. A microelectronic device may be produced by a processcomprising: a) applying an organosilicate glass dielectric film onto asubstrate; b) forming a pattern of vias and/or trenches in theorganosilicate glass dielectric film, and subjecting the organosilicateglass dielectric film to at least one treatment which removes at least aportion of previously existing carbon containing moieties and reduceshydrophobicity of said organosilicate glass dielectric film; c)contacting the organosilicate glass dielectric film with a treatingagent composition at a concentration and for a time period effective toincrease the hydrophobicity of the organosilicate glass dielectric film,wherein the treating agent composition comprises a component capable ofalkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation, an activating agent which may be anamine, an onium compound, an alkali metal hydroxide, and combinationsthereof; and either a miscible mixture of a main solvent as listed aboveand a co-solvent as listed above, or only a co-solvent as listed above;then optionally baking at from about 80° C. to about 500° C. for about10 seconds or more. In one embodiment, baking may be done by heating attemperatures of from about 90° C. to about 450° C. In anotherembodiment, heating may be done at temperatures of from about 100° C. toabout 400° C., in yet another embodiment, heating may be done attemperatures of from about 125° C. to about 350° C. Such heating may bedone for from about 10 seconds or more, preferably for from about 10seconds to about 60 minutes. The next step is d) filling the vias and/ortrenches with a metal by any method known in the art; and then e)optionally subjecting the metal to an annealing treatment. In oneembodiment, annealing may be done by heating the device at temperaturesof from about 150° C. to about 350° C. In another embodiment, annealingmay be done by heating the device at temperatures of from about 200° C.to about 250° C., Annealing may be done for from about 10 seconds toabout 60 minutes.

The microelectronic devices, dielectric layers and materials may beutilized or incorporated into any suitable electronic component.Electronic components, as contemplated herein, are generally thought tocomprise any dielectric component or layered dielectric component thatcan be utilized in an electronic-based product. Contemplated electroniccomponents comprise circuit boards, chip packaging, dielectriccomponents of circuit boards, printed-wiring boards, and othercomponents of circuit boards, such as capacitors, inductors, andresistors.

Electronic-based products can be “finished” in the sense that they areready to be used in industry or by other consumers. Examples of finishedconsumer products are a television, a computer, a cell phone, a pager, apalm-type organizer, a portable radio, a car stereo, and a remotecontrol. Also contemplated are “intermediate” products such as circuitboards, chip packaging, and keyboards that are potentially utilized infinished products.

Electronic products may also comprise a prototype component, at anystage of development from conceptual model to final scale-up mock-up. Aprototype may or may not contain all of the actual components intendedin a finished product, and a prototype may have some components that areconstructed out of composite material in order to negate their initialeffects on other components while being initially tested. Electronicproducts and components may comprise layered materials, layeredcomponents, and components that are laminated in preparation for use inthe component or product.

The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1 2-HEPTANONE+ACETIC ACID

1.257 g of 1% solution of tetramethylammonium acetate (Aldrich ChemicalCompany, Milwaukee, Wis. 53201), 44.24 g of 2-heptanone (Ultra PureSolutions Inc., Castroville, Calif. 85012), and 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were mixedtogether in a 60 ml particle free high density polyethylene bottle. Thesolution was mixed vigorously for one minute. After mixing, the dilutedprecursor was hand filtered to 0.1 μm using a teflon filter.Approximately 2.0-3.0 ml of the formulation was deposited onto an 8″etched (C₄F₈; 20 s.) & ashed (plasma O₂; 20 s.) carbon depleted porousSiCOH film (˜4000 Å thick NANOGLASS-E®). After deposition, the wafer wasspun at 2500 rpm for 30 seconds to form a film. The films were heated atelevated temperatures for 1 min. each at 125° C., 200° C. and 350° C. inN₂ ambient.

The following results were observed: Pre-Etch & Post-Etch & Post TAMeasurement Ash ILD Ash ILD ILD Dielectric 2.34 3.18 2.28 Constant (k)FTIR CH/SiO 71 peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer

The following results were observed: KLA 2132: Defect Density+ 5000counts/cm².

EXAMPLE 2 2-Heptanone+Hexanol

0.0126 g tetramethylammonium acetate (Aldrich Chemical Company,Milwaukee, Wis. 53201), were added to 1.247 g 1-Hexanol, the mix wasstirred until dissolution, then 44.24 g of 2-heptanone (Ultra PureSolutions Inc., Castroville, Calif. 85012), and 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were added in a60 ml particle free high density polyethylene bottle. The solution wasmixed vigorously for one minute. After mixing, the diluted precursor washand filtered to 0.1 μm using a teflon filter. Approximately 2.0-3.0 mlof The formulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.32 Constant (k) FTIR CH/SiO 66peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 224-458 counts/cm².

EXAMPLE 3 Dimethylsulfoxide

0.0126 g tetramethylammonium acetate (Aldrich Chemical Company,Milwaukee, Wis. 53201), were added to 1.247 g dimethylsulfoxide, the mixwas stirred until dissolution, then 44.24 g of 2-heptanone (Ultra PureSolutions Inc., Castroville, Calif. 85012), and 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were added in a60 ml particle free high density polyethylene bottle. The solution wasmixed vigorously for one minute. After mixing, the diluted precursor washand filtered to 0.1 μm using a teflon filter. Approximately 2.0-3.0 mlof The formulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.65 Constant (k) FTIR CH/SiO 34peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 177-885 counts/cm².

EXAMPLE 4 Ethyl Acetoacetate

0.0126 g tetramethylammonium acetate (Aldrich Chemical Company,Milwaukee, Wis. 53201), were added to 45.49 g ethyl acetoacetate, themix was stirred until dissolution, then 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were added in a60 ml particle free high density polyethylene bottle. The solution wasmixed vigorously for one minute. After mixing, the diluted precursor washand filtered to 0.1 μm using a teflon filter. Approximately 2.0-3.0 mlof The formulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.35 Constant (k) FTIR CH/SiO 49peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 237-390 counts/cm².

EXAMPLE 5 2-Heptanone+Dimethylsulfoxide

0.0126 g tetramethylammonium acetate (Aldrich Chemical Company,Milwaukee, Wis. 53201), were added to 1.247 g dimethylsulfoxide, the mixwas stirred until dissolution, then 44.24 g of 2-heptanone (Ultra PureSolutions Inc., Castroville, Calif. 85012), and 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were added in a60 ml particle free high density polyethylene bottle. The solution wasmixed vigorously for one minute. After mixing, the diluted precursor washand filtered to 0.1 μm using a teflon filter. Approximately 2.0-3.0 mlof The formulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.33 Constant (k) FTIR CH/SiO 79peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 227-1520 counts/cm².

EXAMPLE 6 2-Heptanone+Ethyl Acetoacetate

0.0126 g tetramethylammonium acetate (Aldrich Chemical Company,Milwaukee, Wis. 53201), were added to 1.247 g ethyl acetoacetate, themix was stirred until dissolution, then 44.24 g of 2-heptanone (UltraPure Solutions Inc., Castroville, Calif. 85012), and 4.49 g ofdimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) were added in a60 ml particle free high density polyethylene bottle. The solution wasmixed vigorously for one minute. After mixing, the diluted precursor washand filtered to 0.1 μm using a teflon filter. Approximately 2.0-3.0 mlof The formulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.30 Constant (k) FTIR CH/SiO 82peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 0.9-1.8 counts/cm².

EXAMPLE 7 2-Heptanone+Ethyl Acetoacetate

37.6 g of 0.255% solution of tetramethylammonium acetate (AldrichChemical Company, Milwaukee, Wis. 53201), in Ethyl acetoacetate (0.359 gtetramethylammonium acetate+140.00 g Ethyl acetoacetate) were added by84.90 g of 0.5% solution of tetrabutylammonium acetate in 2-Heptanone(2.175 g tetrabutylammonium acetate+435 g 2-Heptanone), 1242.50 g2-Heptanone (Ultra Pure Solutions Inc., Castroville, Calif. 85012), and135 g of dimethyldiacetoxysilane (Gelest, Tullytone, Pa. 19007) wereadded in a 2 L particle free high density polyethylene bottle. Thesolution was mixed vigorously for one minute. After mixing, the dilutedprecursor was subjected to 2-pass filtration using 0.04 micron filter(Meissner CSPM0.04-442). Approximately 2.0-3.0 ml of The formulation wasdeposited onto an 8″ etched (C₄F₈; 20 s.) & ashed (plasma O₂; 20 s.)carbon depleted porous SiCOH film (˜4000 Å thick NANOGLASS-E®). Afterdeposition, the wafer was spun at 2500 rpm for 30 seconds to form afilm. The films were heated at elevated temperatures for 1 min. each at125° C., 200° C. and 350° C. in N₂. The following results were observed:Pre-Etch & Post-Etch & Post TA Measurement Ash ILD Ash ILD ILDDielectric 2.34 3.18 2.21 Constant (k) FTIR CH/SiO 96 peak restoration,%

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 1.7-1.9 counts/cm².

EXAMPLE 8 2-Heptanone+Ethyl Acetoacetate

37.6 g of 0.255% solution of tetramethylammonium acetate (AldrichChemical Company, Milwaukee, Wis. 53201), in Ethyl acetoacetate (0.359 gtetramethylammonium acetate+140.00 g Ethyl acetoacetate) were added by84.90 g of 0.5% solution of tetrabutylammonium acetate in 2-Heptanone(2.175 g tetrabutylammonium acetate+2-Heptanon to weight 435.00 g),1242.50 g 2-Heptanone (Ultra Pure Solutions Inc., Castroville, Calif.85012), and 135.00 g of dimethyldiacetoxysilane (Gelest, Tullytone, Pa.19007) were added in a 2 L particle free high density polyethylenebottle. The solution was mixed vigorously for one minute. After mixing,the diluted precursor was subjected to 2-pass filtration using 0.04micron filter (Meissner CSPM0.04-442). Approximately 2.0-3.0 ml of Theformulation was deposited onto an 8″ etched (C₄F₈; 20 s.) & ashed(plasma O₂; 20 s.) carbon depleted porous SiCOH film (˜4000 Å thickNANOGLASS-E®). After deposition, the wafer was spun at 2500 rpm for 30seconds to form a film. The films were heated at elevated temperaturesfor 1 min. each at 125° C., 200° C. and 350° C. in N₂. The followingresults were observed: Pre-Etch & Post-Etch & Post TA Measurement AshILD Ash ILD ILD Dielectric 2.34 3.18 2.35 Constant (k) FTIR CH/SiO 96peak restoration, %

In a similar way 2.0-3.0 ml of the formulation was deposited, spun andbaked onto an 8″ Si-wafer. The following results were observed: KLA 2132Defect Density 20.6 counts/cm².

While the present invention has been particularly shown and describedwith reference to preferred embodiments, it will be readily appreciatedby those of ordinary skill in the art that various changes andmodifications may be made without departing from the spirit and scope ofthe invention. It is intended that the claims be interpreted to coverthe disclosed embodiment, those alternatives which have been discussedabove and all equivalents thereto.

1. A composition for treating an organosilicate glass dielectric filmwhich comprises a) a component capable of alkylating or arylatingsilanol moieties of an organosilicate glass dielectric film viasilylation, b) an activating agent and c) a mixture of a main solventand a co-solvent, wherein the mixture solubilizes the component capableof alkylating or arylating silanol moieties of the organosilicate glassdielectric film via silylation and the activating agent; and wherein theco-solvent has a higher vapor pressure and/or boiling point than themain solvent.
 2. The composition of claim 1 wherein the activating agentcomprises one or more acids, bases, onium compounds, dehydrating agents,or combinations thereof
 3. The composition of claim 1 wherein theco-solvent has a boiling point of from about 1° C. to about 100° C.higher than the main solvent.
 4. The composition of claim 1 wherein theco-solvent has a boiling point of from about 10° C. to about 70° C.higher than the main solvent.
 5. The composition of claim 1 wherein theco-solvent has a boiling point of from about 20° C. to about 50° C.higher than the main solvent.
 6. The composition of claim 1 wherein themain solvent comprises one or more ketones, ethers, esters,hydrocarbons, alcohols, carboxylic acids, amines, amides, orcombinations thereof.
 7. The composition of claim 1 wherein theco-solvent comprises ethylacetoacetate, methyl acetoacetate, t-butylacetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate, benzylacetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthylacetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzylacetate, dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1,2-dichlorobenzene, chlorotoluene,1-hexanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 6-phenyl-1-hexanol,1-heptanol, 2-heptanol, 4-heptanol, 4-methyl-3-heptanol,6-methyl-2-heptanol, 2,6-dimethylheptanol, 1-octanol, or combinationsthereof.
 8. The composition of claim 1 wherein the co-solvent comprisesethylacetoacetate, dimethylsulfoxide, 1-hexanol, N,N-dimethylacetamideor combinations thereof.
 9. The composition of claim 1 wherein themixture comprises 2-heptanone and ethylacetoacetate.
 10. The compositionof claim 1 wherein the main solvent is present in the mixture in anamount of from about 0.1 to about 99.9 based on the percent by weight ofthe mixture.
 11. The composition of claim 1 wherein the co-solvent ispresent in the mixture in an amount of from about 0.1 to about 99.9based on the percent by weight of the mixture.
 12. The composition ofclaim 1 wherein the activating agent comprises one or more amines,ammonium compounds, phosphonium compounds, sulfonium compounds, iodoniumcompounds, hydroxides, alkoxides, acid halides, silanolates, aminesalts, or combinations thereof.
 13. The composition of claim 1 whereinthe activating agent comprises one or more alkyl amines, aryl amines,alcohol amines, or combinations thereof.
 14. The composition of claim 1wherein the activating agent comprises one or more primary amines,secondary amines, tertiary amines, ammonia, quaternary ammonium salts,or combinations thereof.
 15. The composition of claim 1 wherein theactivating agent comprises tetramethylammonium acetate,tetrabutylammonium acetate or combinations thereof.
 16. The compositionof claim 1 wherein the activating agent comprises hydrochloric acid,sulfuric acid, nitric acid, boric acid, ethylsulfuric acid,chlorosulfuric acid, phosphonitrile chloride, iron chloride, zincchloride, tin chloride, aluminum chloride, boron trifluoride,methanesulfonic acid, trifluoromethanesulfonic acid, iron chloridehexahydrate or combinations thereof.
 17. The composition of claim 1wherein the activating agent comprises one or more phosphorous halides,phosphorous pentoxide, phenylphosphonic dichloride, and phenylphosphorodichloridate, or combinations thereof.
 18. The composition ofclaim 1 wherein the activating agent comprises sodium hydroxide, cesiumhydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide,or combinations thereof.
 19. The composition of claim 1 wherein thecomponent capable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation comprises at leastone compound having a formula [—SiR₂NR′—]n where n>2 and may be cyclic;R₃SiNR′SiR₃, (R₃Si)₃N; R₃SiNR′₂; R₂Si(NR′)₂; RSi(NR′)₃; R_(x)SiCl_(y),R_(x)Si(OH)_(y); R₃SiOSiR′₃; R_(x)Si(OR′)_(y); R_(x)Si(OCOR′)_(y);R_(x)SiH_(y); R_(x)Si[OC(R′)═R″]_(4-x) or combinations thereof, whereinx is an integer ranging from 1 to 3, y is an integer ranging from 1 to 3such that y=4-x, each R is independently selected from hydrogen and ahydrophobic organic moiety; R′ is hydrogen, or an organic moiety, and R″is an alkyl or carbonyl group.
 20. The composition of claim 1 whereinthe component capable of alkylating or arylating silanol moieties of aorganosilicate glass dielectric film via silylation comprisesdimethyldiacetoxysilane
 21. The composition of claim 1 wherein thecomponent capable of alkylating or arylating silanol moieties of aorganosilicate glass dielectric film via silylation comprisesdimethyldiacetoxysilane and the activating agent comprises a combinationof tetramethyl ammonium acetate and tetrabutyl ammonium acetate.
 22. Thecomposition of claim 1 further comprising a corrosion inhibitor.
 23. Acomposition for treating an organosilicate glass dielectric film whichcomprises a) a component capable of alkylating or arylating silanolmoieties of the organosilicate glass dielectric film via silylation, b)an activating agent; and c) a solvent which solubilizes the componentcapable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation, and the activatingagent, which solvent comprises ethylacetoacetate, methyl acetoacetate,t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate,phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate,alpha-methylbenzyl acetate, dimethylsulfoxide,N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.
 24. Thecomposition of claim 23 wherein the activating agent comprises one ormore acids, bases, onium compounds, dehydrating agents, or combinationsthereof
 25. A method which comprises: a) forming an organosilicate glassdielectric film; b) contacting the organosilicate glass dielectric filmwith a composition which comprises a component capable of alkylating orarylating silanol moieties of the organosilicate glass dielectric filmvia silylation; an activating agent; and a solvent which comprises (i)or (ii): (i) a mixture of a main solvent and a co-solvent, which mixtureis capable of solubilizing the component capable of alkylating orarylating silanol moieties of the organosilicate glass dielectric filmvia silylation and the activating agent; which co-solvent has a highervapor pressure and/or boiling point than the main solvent; (ii)ethylacetoacetate, methyl acetoacetate, t-butyl acetoacetate,2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate,nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthyl acetate,2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate,dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,1,2-dichlorobenzene, chlorotoluene, N,N-diethylacetamide,N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.
 26. The methodof claim 25 wherein the activating agent comprises one or more acids,bases, onium compounds, dehydrating agents, or combinations thereof. 27.The method of claim 25 further comprising the subsequent step of heatingthe organosilicate glass dielectric film.
 28. The method of claim 25wherein the organosilicate glass dielectric film is porous.
 29. Themethod of claim 25 wherein the organosilicate glass dielectric film issubstantially non-porous.
 30. The method of claim 25 further comprisingthe subsequent steps of: d) optionally baking at from about 80° C. toabout 400° C. for about 10 seconds or more; thereafter e) filling thevias and/or trenches with a metal; and thereafter f) optionallysubjecting the metal to an annealing treatment.
 31. The method of claim25 wherein the component capable of alkylating or arylating silanolmoieties of a organosilicate glass dielectric film via silylationcomprises dimethyldiacetoxysilane
 32. The method of claim 25 wherein thecomponent capable of alkylating or arylating silanol moieties of aorganosilicate glass dielectric film via silylation comprisesdimethyldiacetoxysilane and the activating agent comprises a combinationof tetramethyl ammonium acetate and tetrabutyl ammonium acetate.
 33. Amethod for deterring the formation of stress-induced voids in anorganosilicate glass dielectric film on a substrate, whichorganosilicate glass dielectric film has been subjected to at least onestep which removes at least a portion of previously existing carboncontaining moieties or reduces hydrophobicity of said organosilicateglass dielectric film, comprising contacting the organosilicate glassdielectric film, after being subjected to at least one step whichremoves at least a portion of previously existing carbon containingmoieties or reduces hydrophobicity of said organosilicate glassdielectric film, with a composition at a concentration and for a timeperiod effective to restore at least some of the carbon containingmoieties hydrophobicity or increase the hydrophobicity of theorganosilicate glass dielectric film, wherein the composition comprises:a) a component capable of alkylating or arylating silanol moieties of aorganosilicate glass dielectric film via silylation, b) an activatingagent and c) a solvent which comprises (i) or (ii): (i) a mixture of amain solvent and a co-solvent, which mixture is capable of solubilizingthe component capable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation and the activatingagent; which co-solvent has a higher vapor pressure and/or boiling pointthan the main solvent; (ii) ethylacetoacetate, methyl acetoacetate,t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate,phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate,alpha-methylbenzyl acetate, dimethylsulfoxide,N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.
 34. The methodof claim 33 wherein the activating agent comprises one or more acids,bases, onium compounds, dehydrating agents, or combinations thereof 35.A method for forming a microelectronic device which comprises: a)forming an organosilicate glass dielectric film on a substrate; b)subjecting the organosilicate glass dielectric film to at least one stepwhich removes at least a portion of previously existing carboncontaining moieties or reduces hydrophobicity of said organosilicateglass dielectric film; c) contacting the organosilicate glass dielectricfilm with a composition at a concentration and for a time periodeffective to restore at least a portion of previously existing carboncontaining moieties or increase the hydrophobicity of the organosilicateglass dielectric film, wherein the composition comprises a componentcapable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation; an activatingagent; and a solvent which comprises (i) or (ii): (i) a mixture of amain solvent and a co-solvent, which mixture is capable of solubilizingthe component capable of alkylating or arylating silanol moieties of theorganosilicate glass dielectric film via silylation and the activatingagent; which co-solvent has a higher vapor pressure and/or boiling pointthan the main solvent; (ii) ethylacetoacetate, methyl acetoacetate,t-butyl acetoacetate, 2-methoxyethyl acetoacetate, allyl acetoacetate,benzyl acetoacetate, nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate,phenthyl acetate, 2-butoxyethyl acetate, 2-ethylhexyl acetate,alpha-methylbenzyl acetate, dimethylsulfoxide,N-methyl-N-methoxyacetamide, N,N-diethyl-2-phenylacetamide,N,N-dimethylacetamide, 1,2-dichlorobenzene, chlorotoluene,N,N-diethylacetamide, N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.
 36. The methodof claim 35 further comprising the subsequent steps of: d) optionallybaking at from about 80° C. to about 400° C. for about 10 seconds ormore; thereafter e) filling the vias and/or trenches with a metal; andthereafter f) optionally subjecting the metal to an annealing treatment.37. The method of claim 35 wherein the activating agent comprises one ormore acids, bases, onium compounds, dehydrating agents, or combinationsthereof.
 38. A microelectronic device produced by the method of claim35.
 39. A method for forming a microelectronic device which comprises:a) forming an organosilicate glass dielectric film on a substrate; b)forming a pattern of vias and/or trenches in the organosilicate glassdielectric film, and subjecting the organosilicate glass dielectric filmto at least one treatment which removes at least a portion of previouslyexisting carbon containing moieties or reduces hydrophobicity of saidorganosilicate glass dielectric film; and thereafter c) contacting theorganosilicate glass dielectric film with a composition at aconcentration and for a time period effective to restore at least aportion of previously existing carbon containing moieties or increasethe hydrophobicity of the organosilicate glass dielectric film, whereinthe composition comprises a component capable of alkylating or arylatingsilanol moieties of the organosilicate glass dielectric film viasilylation; an activating agent; and a solvent which comprises (i) or(ii): (i) a mixture of a main solvent and a co-solvent, which mixture iscapable of solubilizing the component capable of alkylating or arylatingsilanol moieties of the organosilicate glass dielectric film viasilylation and the activating agent; which co-solvent has a higher vaporpressure and/or boiling point than the main solvent; (ii)ethylacetoacetate, methyl acetoacetate, t-butyl acetoacetate,2-methoxyethyl acetoacetate, allyl acetoacetate, benzyl acetoacetate,nonyl acetate, 2-(2-butoxyethoxy)ethyl acetate, phenthyl acetate,2-butoxyethyl acetate, 2-ethylhexyl acetate, alpha-methylbenzyl acetate,dimethylsulfoxide, N-methyl-N-methoxyacetamide,N,N-diethyl-2-phenylacetamide, N,N-dimethylacetamide,1,2-dichlorobenzene, chlorotoluene, N,N-diethylacetamide,N,N-diphenylacetamide, N,N-dimethypropionamide,N,N-dimethylisobutyramide, 1-hexanol, 2-ethyl-1-hexanol,5-methyl-1-hexanol, 6-phenyl-1-hexanol, 1-heptanol, 2-heptanol,4-heptanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol,2,6-dimethylheptanol, 1-octanol, or combinations thereof.
 40. The methodof claim 39 further comprising the subsequent steps of: d) optionallybaking at from about 80° C. to about 400° C. for about 10 seconds ormore; thereafter e) filling the vias and/or trenches with a metal; andthereafter f) optionally subjecting the metal to an annealing treatment.41. The method of claim 39 wherein the activating agent comprises one ormore acids, bases, onium compounds, dehydrating agents, or combinationsthereof.
 42. A microelectronic device produced by the method of claim39.